Coal Utilization By-products Research Articles

Influence of the Anionic Zinc-Adeninate Metal-Organic Framework Structure on the Luminescent Detection of Rare Earth Ions in Aqueous Streams.

Rare earth elements (REEs) are critical to numerous technologies; however, a combination of increasing demand, environmental concerns, and monopolistic marketplace conditions has spurred interest in boosting the domestic REE production from sources such as coal utilization byproducts. The economic viability of this approach requires rapid, inexpensive, and sensitive analytical techniques capable of characterizing the REE content during resource exploration and downstream REE processing (e.g., analyzing REE separation, concentration, and purification production steps). Luminescence-based sensors are attractive because many REEs may be sensitized to produce element-specific emission. Hence, a single material may simultaneously detect and distinguish multiple REEs. Metal-organic frameworks (MOFs) can sensitize multiple REEs, but their viability has been hindered by sensitivity and selectivity challenges. Understanding how the MOF structure impacts the REE sensing efficacy is critical to the rational design of new sensors. Here, we evaluate the sensing performance of seven different anionic zinc-adeninate MOFs with different organic linkers and/or structures for the visible-emitting REEs Tb, Dy, Sm, and Eu. The choice of a linker determines which REEs are sensitized and significantly influences their sensitivity and selectivity against competing species (here, Fe(II) and HCl). For a given linker, structural changes to the MOF can further fine-tune the performance. The MOFs produce some of the lowest detection limits (sub-10 ppb for Tb) reported for the aqueous sensitization-based REE detection. Importantly, the most selective MOFs demonstrated the ability to sensitize the REE signal at sub-ppm levels in a REE-spiked acid mine drainage matrix, highlighting their potential for use in real-world sensing applications.

Advanced characterization of rare earth element minerals in coal utilization byproducts using multimodal image analysis

Multimodal microanalytical characterization techniques are applied to identify and quantify rare earth element (REE) and REE + Y (REY) bearing mineral phases in coal utilization byproducts (CUB) from various coal-fired power plants. The characterization work provides quantitative assessments of REE in coal and CUB as obtained from 2- and 3D imaging, elemental mapping, volumetric estimates, and advanced high-resolution pixel classification. REY-bearing phosphate minerals rhabdophane (Ce,La)(PO4·H2O), monazite (Ce,La,Nd,Th)(PO4,SiO4), xenotime (YPO4,SiO4), and apatite (Ca5(PO4)3(F,Cl,OH), as well as REE-enriched calcium oxide were identified via electron microscopy and microprobe analysis. The minerals generally occurred as 1–20 μm-long crystals in the rock and ash samples. The most notable finding was that REEs are present as monomineralic grains dispersed within the ash, as well as fused to or encapsulated by amorphous aluminosilicate glass particles, also referred to as slag. It is indicative that conventional coal combustion processes sequester REE-bearing mineral phases such as rhabdophane, monazite, and zircon from the coal feed into aluminosilicate glass phases. The advanced microscopy and image analysis techniques applied in this study make it possible to deduce the average density of ash particles and quantify REE phases encapsulated in glass. Consequently, these REE phases may be targeted and recovered via density separation. These findings advance resource recovery techniques and commercial REE separation technologies for coal and combustion byproducts.

Coal and coal byproducts: A large and developable unconventional resource for critical materials – Rare earth elements

Rare earth elements (REEs) are critical materials and provide significant values to national security, energy production, environmental protection and economic growth. The supply of REEs in U.S. solely relies on import as domestic production of REEs was ceased because of the environmental concerns during mining and lack of competitiveness. Nonetheless, unconventional REEs-containing resources, including produced water, acid mine drainage, and coal and coal byproducts (C&CBs) contain significant amounts of REEs. However, the concentrations of REEs in these resources are several orders of magnitude lower than that of REEs ores. Thus, extraction of REEs from these materials is challenging. Here we report REEs extraction with environmentally friendly method that successfully concentrated REEs from 312 ppm in fly ash to 99.4% in the final product. Especially, the five critically important REEs (Dy, Eu, Nd, Tb, and Y) account for up to ∼63% of the total weight of all REEs in the final 99.4%-purity product. Coal fly ash is one of the major solid coal utilization byproducts, representing great potential resources for REEs extraction. Extraction of REEs from these unconventional resources could be the way to secure domestic supply of these critical materials.

Strontium Isotope Study of Coal Utilization By-Products Interacting with Environmental Waters

Sequential leaching experiments on coal utilization by-products (CUB) were coupled with chemical and strontium (Sr) isotopic analyses to better understand the influence of coal type and combustion processes on CUB properties and the release of elements during interaction with environmental waters during disposal. Class C fly ash tended to release the highest quantity of minor and trace elements-including alkaline earth elements, sodium, chromium, copper, manganese, lead, titanium, and zinc-during sequential extraction, with bottom ash yielding the lowest. Strontium isotope ratios ((87)Sr/(86)Sr) in bulk-CUB samples (total dissolution of CUB) are generally higher in class F ash than in class C ash. Bulk-CUB ratios appear to be controlled by the geologic source of the mineral matter in the feed coal, and by Sr added during desulfurization treatments. Leachates of the CUB generally have Sr isotope ratios that are different than the bulk value, demonstrating that Sr was not isotopically homogenized during combustion. Variations in the Sr isotopic composition of CUB leachates were correlated with mobility of several major and trace elements; the data suggest that arsenic and lead are held in phases that contain the more radiogenic (high-(87)Sr/(86)Sr) component. A changing Sr isotope ratio of CUB-interacting waters in a disposal environment could forecast the release of certain strongly bound elements of environmental concern. This study lays the groundwork for the application of Sr isotopes as an environmental tracer for CUB-water interaction.

Tracing the interaction of acid mine drainage with coal utilization byproducts in a grouted mine: Strontium isotope study of the inactive Omega Coal Mine, West Virginia (USA)

Abstract In order to ameliorate acidic discharge, the inactive Omega Coal Mine, West Virginia was partially filled by injection of a grout consisting of 98% coal utilization byproducts (CUB), including fluidized bed combustion ash and fly ash, and 2% Portland cement. In this study, discharge chemistry and Sr isotope ratios were determined to identify and quantify the extent of interaction between mine waters and the CUB–cement grout. Eight sampling sites were monitored around the downdip perimeter of the mine. The major and trace element chemistry of the discharges was generally not sufficient to distinguish between discharges that interacted with grout and those that did not. Elements that showed the most separation include K and As, which were elevated in some waters that interacted with CUB–cement grout. In contrast, the Sr isotope ratios clearly distinguished discharges from grouted and non-grouted areas. Discharges that bypassed the grouted portions had 87 Sr/ 86 Sr ratios ranging from 0.71510 to 0.71594, while two discharges that interacted with grout had ratios in the range of 0.71401–0.71456. The Treatment Inlet, which includes both grouted and ungrouted discharges, yielded intermediate isotopic ratios. Leaching experiments on CUB–cement grout, coal and surrounding rocks are consistent with the isotopic trends observed in the discharges. Based on these results, waters that interacted with grout received 30–40% of their Sr from the CUB–cement grout material. These results suggest that the grout material is chemically eroding at a rate of approximately 0.04% per year. This novel application of the Sr isotope system illustrates its ability to sensitively track and quantify fluid interaction with coal and CUB-based grout.

Serial batch leaching procedure for characterization of coal fly ash

Although many leaching methods have been used for various purposes by research groups, industries, and regulators, there is still a need for a simple but comprehensive approach to leaching coal utilization by-products and other granular materials in order to estimate potential release of heavy metals when these materials are exposed to natural fluids. A serial batch characterization method has been developed at the National Energy Technology Laboratory that can be completed in 2-3 days to serve as a screening tool. The procedure provides an estimate of cumulative metals release under varying pH conditions, and leaching the sample at increasing liquid/solid ratios can indicate the rate at which this process will occur. This method was applied to eight fly ashes, adapted to the acidic or alkaline nature of the ash. The leachates were analyzed for 30 elements. The test was run in quadruplicate, and the relative standard deviation (RSD) was used as a measure of method reproducibility. RSD values are between 0.02 and 0.70, with the majority of the RSD values less than 0.3. The serial batch leaching procedure was developed as a simple, relatively quick, yet comprehensive method of estimating the risk of heavy metal release from fly ash when it is exposed to natural fluids, such as acid rain or groundwater. Tests on a random selection of coal fly ashes have shown it to be a reasonably precise method for estimating the availability and long-term release of cations from fly ash.

Soluble metals in coal gasification residues

The By-Product Utilization Team at the National Energy Technology Laboratory (NETL) of the US Department of Energy has conducted column leaching tests to characterize the release of various cations from coal utilization by-products (CUB). The release of metals from the nine samples of residues generated in three coal integrated gasification combined cycle (IGCC) installations was determined. Cations tended to be more soluble than from PC fly ash samples. Except for Hg, total cation solubility was due to the relatively high concentration in a few leachate samples. For several IGCC by-product samples generated from a mixture of coal and pet coke, the amount of As, Ni, and Zn extracted from the IGCC residues exceeded primary or secondary drinking water standards in the early leachate samples.

Environmental chamber measurements of mercury flux from coal utilization by-products

An environmental chamber was constructed to measure the mercury flux from coal utilization by-product (CUB) samples. Samples of fly ash, FGD gypsum, and wallboard made from FGD gypsum were tested under both dark and illuminated conditions with or without the addition of water to the sample. Mercury releases varied widely, with 7-day experiment averages ranging from −6.8 to 73 ng/m 2 h for the fly ash samples and −5.2 to 335 ng/m 2 h for the FGD/wallboard samples. Initial mercury content, fly ash type, and light exposure had no observable consistent effects on the mercury flux. For the fly ash samples, the effect of a mercury control technology was to decrease the emission. For three of the four pairs of FGD gypsum and wallboard samples, the wallboard sample released less (or absorbed more) mercury than the gypsum.

Scatterscore: A Reconnaissance Method To Evaluate Changes In Water Quality

Water quality data collected in periodic monitoring programs are often difficult to evaluate, especially if the number of parameters is large, the sampling schedule varies, and values are of different orders of magnitude. The Scatterscore Water Quality Evaluation was developed to yield a quantitative score, based on all measured variables in periodic water quality reports, indicating positive, negative or random change. This new methodology calculates a reconnaissance score based on the differences between up-gradient (control) versus down-gradient (treatment) water quality data sets. All parameters measured over a period of time at two or more sampling points are compared. The relationship between the ranges of measured values and the ratio of the medians for each parameter produces a data point that falls into one of four sections on a scattergram. The number and average values of positive, negative and random change points is used to calculate a Scatterscore that indicates the magnitude and direction of overall change in water quality. The Scatterscore Water Quality Evaluation, a reconnaissance method to track general changes, has been applied to 20 sites at which coal utilization by-products (CUB) were used to control acid mine drainage (AMD).

Relative solubility of cations in Class F fly ash.

Coal utilization byproducts (CUB), such as fly ash, contain cations that may be released during exposure to fluids such as acid rain or acid mine drainage. Researchers at the Department of Energy's National Energy Technology Laboratory (DOE/NETL) have conducted a long-term column leaching study of 32 Class F fly ash samples from pulverized coal (PC) combustion, and quantified the release of 19 cations in four leachants with a pH between 1.2 and 12. The relative solubility (M(L/T)) of each cation was defined as the total mass leached (M(L)) relative to the concentration (M(T)) of that element in the fly ash sample. A frequency distribution of relative solubility values was computed with ranges defined as insoluble, slightly soluble, moderately soluble, and very soluble. On the basis of this sample set, Ba, Cd, Fe, Pb, Sb, and Se in PC fly ash are insoluble. The elements Al, Be, Ca, Co, Cr, Cu, K, Mg, Mn, Na, Ni, and Zn are slightly to moderately acid soluble. Only Ca and Na are water soluble; As and Ca are soluble in the basic solution, The results of this study indicate that the extent to which cations in Class F PC fly ash can be leached by naturally occurring fluids is very limited.